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EP0111957B1 - Method of applying a metallic coating to a substrate - Google Patents

Method of applying a metallic coating to a substrate Download PDF

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Publication number
EP0111957B1
EP0111957B1 EP83201703A EP83201703A EP0111957B1 EP 0111957 B1 EP0111957 B1 EP 0111957B1 EP 83201703 A EP83201703 A EP 83201703A EP 83201703 A EP83201703 A EP 83201703A EP 0111957 B1 EP0111957 B1 EP 0111957B1
Authority
EP
European Patent Office
Prior art keywords
substrate
layer
hydrophilic
adhesion
bonding agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP83201703A
Other languages
German (de)
French (fr)
Other versions
EP0111957A2 (en
EP0111957A3 (en
Inventor
Johannes J. Ponjeé
Johan W.A. Nelissen
Christiaan J. A. Verwijlen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Koninklijke Philips NV
Original Assignee
Philips Gloeilampenfabrieken NV
Koninklijke Philips Electronics NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Philips Gloeilampenfabrieken NV, Koninklijke Philips Electronics NV filed Critical Philips Gloeilampenfabrieken NV
Publication of EP0111957A2 publication Critical patent/EP0111957A2/en
Publication of EP0111957A3 publication Critical patent/EP0111957A3/en
Application granted granted Critical
Publication of EP0111957B1 publication Critical patent/EP0111957B1/en
Expired legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B23/00—Record carriers not specific to the method of recording or reproducing; Accessories, e.g. containers, specially adapted for co-operation with the recording or reproducing apparatus ; Intermediate mediums; Apparatus or processes specially adapted for their manufacture
    • G11B23/0057—Intermediate mediums, i.e. mediums provided with an information structure not specific to the method of reproducing or duplication such as matrixes for mechanical pressing of an information structure ; record carriers having a relief information structure provided with or included in layers not specific for a single reproducing method; apparatus or processes specially adapted for their manufacture
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/38—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal at least one coating being a coating of an organic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating

Definitions

  • the invention relates to a method for applying a metal layer adhering to a substrate by means of an adhesion promoter made from an alkoxysilylalkylthiol, an alkoxysilylalkylamine or a chorsilylalkylthiol.
  • Such a method is known from DE-OS-30 16 560, where an alkoxysilylalalkylthiol, an alkoxysilylalalkylamine or a chlorosilylalkylthiol is used as the adhesion promoter.
  • the molecule of this adhesion promoter adheres to the substrate on one side, the silicate side. This brings the sulfur or amine group to the outside, so that good adhesion with metals is obtained.
  • the adhesion promoter When the adhesion promoter is applied as such or in the form of a solution by dipping or spraying, the compound is polymerized. If necessary, a base layer based on a polysiloxane is applied before the adhesion promoter is attached.
  • micro-profiling is a digital information pattern in the form of depressions with differently designed surface areas on the order of 1 IJ.m2 with an accuracy of 0.1 w m 2 .
  • the object of the invention is to apply a metal layer on a substrate in such a way that an ultra-smooth or micro-profiled substrate surface is reproducibly retained in the attached metal layer.
  • the adhesion promoter is applied as a monomer in a layer which is at most 15 molecules thick on the substrate surface which is either already hydrophilic or has previously been made hydrophilic by contact with an atmosphere in which the adhesion promoter is present in vapor form , and that the metal layer is then applied with a thickness of 50-300 nm.
  • the layer of the adhesion promoter is preferably applied in a monomolecular layer.
  • the substrate with which the process can be carried out successfully must be hydrophilic or made hydrophilic in order to ensure good adhesion with the alkoxylated silane groups.
  • Most plastics are not hydrophilic per se, but can be made hydrophilic by an oxidizing pretreatment.
  • a polycarbonate can be made hydrophilic by treatment with a dilute bichromate sulfuric acid solution.
  • the starting point is an aluminum substrate, the surface of which has been smoothed by conventional machining, for example using a normal lathe, and consequently has a fairly high roughness from a microscopic point of view.
  • a quartz gauge the surface of which has an ultra-smooth profile
  • the surface of the substrate is filled with a plastic, for example an acrylate, in the depressions, the plastic is polymerized by means of UV radiation and in this way brought to the same high degree of smoothness as the quartz glass .
  • the substrate is then subjected to an oxidizing pretreatment, for example the above-mentioned glow discharge in an oxygen atmosphere. As a result, the plastic parts of the surface are oxidized and at the same time they are cleaned.
  • a thin layer of silver or gold is applied, for example by vapor deposition.
  • Such a mirror is used for example in an IR night vision device.
  • the thickness of the metal layer to be applied by vapor deposition depends on the specific embodiment.
  • a layer of 50-100 nm is deposited.
  • the layer can be thicker - up to 300 nm.
  • the covered matrix is then photopolymerized by exposure to the quartz matrix.
  • the exposed layer is firmly attached to an aluminum substrate and the whole is then removed from the die.
  • the substrate is covered with a plastic covering. see whose surface profile exactly corresponds to that of the die.
  • the hydrophobic plastic surface is then released by a glow discharge in a Saü made plasma hydrophilic for 30 minutes with an alternating voltage of 3-4 kV.
  • the partial vapor tension of the 3-mercaptopropyltrimethoxysilane is sufficient to react with the hydrophilic surface of the object.
  • the adherence of the gold layer to the plastic surface is tested according to the so-called «diamond scratching method» (DIN 53 151) as follows.
  • the adhesiveness of the gold layer on the plastic surface according to the above example could be rated with the rating grade O (optimal adhesion).
  • Example 1 also applies to this example, with the exception that instead of gold, silver is applied to the substrate provided with the polymer layer and the adhesion promoter attached to it.
  • the optimum adhesion of the noble metal to the silicon wafer remains unchanged, even if the metallized wafer has been heated at a temperature of 170 ° C. for 14 days.
  • the large difference in the coefficient of expansion between the Si and the noble metal is thus easily compensated for by the adhesive layer according to the invention.

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  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Laminated Bodies (AREA)
  • Formation Of Insulating Films (AREA)
  • Physical Vapour Deposition (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
  • Preparing Plates And Mask In Photomechanical Process (AREA)

Description

Die Erfindung bezieht sich auf ein Verfahren zum Anbringen einer auf einem Substrat haftenden Metallschicht mittels eines Haftvermittlers aus einem Alkoxysilylalkylthiol, einem Alkoxysilylalkylamin oder einem Chorsilylalkylthiol.The invention relates to a method for applying a metal layer adhering to a substrate by means of an adhesion promoter made from an alkoxysilylalkylthiol, an alkoxysilylalkylamine or a chorsilylalkylthiol.

Aus der DE-OS-30 16 560 ist ein derartiges Verfahren bekannt, wpbei als Haftvermittler ein Alkoxysilylalalkylthiol, ein Alkoxysilylalalkylamin oder ein Chlorsilylalkylthiol verwendet wird. Das Molekül dieses Haftvermittlers heftet sich auf einer Seite, der Silikatseite an das Substrat. Dadurch gelangt die Schwefel- bzw. Amingruppe auf die Aussenseite, so dass eine gute Haftung mit Metallen erhalten wird.Such a method is known from DE-OS-30 16 560, where an alkoxysilylalalkylthiol, an alkoxysilylalalkylamine or a chlorosilylalkylthiol is used as the adhesion promoter. The molecule of this adhesion promoter adheres to the substrate on one side, the silicate side. This brings the sulfur or amine group to the outside, so that good adhesion with metals is obtained.

Beim Anbringen des Haftvermittlers als solchem oder in Form einer Lösung durch Tauchen oder Spritzen wird die Verbindung polymerisiert. Gegebenenfalls wird vor dem Anbringen des Haftvermittlers eine Basisschicht auf Basis eines Polysiloxans angebracht.When the adhesion promoter is applied as such or in the form of a solution by dipping or spraying, the compound is polymerized. If necessary, a base layer based on a polysiloxane is applied before the adhesion promoter is attached.

Es besteht jedoch das Bedürfnis, eine dünne Metallschicht fest anzubringen auf einem Substrat, dessen Oberfläche ultraglatt poliert oder mikroprofiliert ist, wobei das Profil nach dem Anbringen der Metallschicht erhalten bleiben soll. Ein Beispiel der genannten Mikroprofilierung ist ein digitales Informationsmuster in Form von Vertiefungen mit unterschiedlich gestalteten Oberflächenbereichen in der Grössenordnung von 1 IJ.m2 bei einer Genauigkeit von 0,1 wm2.However, there is a need to firmly attach a thin metal layer on a substrate, the surface of which is ultra-smooth polished or micro-profiled, and the profile should be retained after the metal layer has been applied. An example of the micro-profiling mentioned is a digital information pattern in the form of depressions with differently designed surface areas on the order of 1 IJ.m2 with an accuracy of 0.1 w m 2 .

Mit Hilfe eines auf übliche Weise aufgetragenen Siloxanharzes kann dies nicht erreicht werden.This cannot be achieved with the aid of a siloxane resin applied in the usual way.

Der Erfindung liegt die Aufgabe zugrunde, eine Metallschicht auf einem Substrat derart anzubringen, dass eine ultraglatte oder mikroprofilierte Substratoberfläche in der angebrachten Metallschicht reproduzierbar erhalten bleibt.The object of the invention is to apply a metal layer on a substrate in such a way that an ultra-smooth or micro-profiled substrate surface is reproducibly retained in the attached metal layer.

Diese Aufgabe wird erfindungsgemäss dadurch gelöst, dass auf der Substratoberfläche, die entweder bereits hydrophil ist oder vorher hydrophil gemacht wird, der Haftvermittler als Monomer in einer höchstens 15 Moleküle dicken Schicht angebracht wird durch Kontakt mit einer Atmosphäre, in der der Haftvermittler in Dampfform vorhanden ist, und dass darauf dann die Metallschicht mit einer Dicke von 50-300 nm angebracht wird.This object is achieved according to the invention in that the adhesion promoter is applied as a monomer in a layer which is at most 15 molecules thick on the substrate surface which is either already hydrophilic or has previously been made hydrophilic by contact with an atmosphere in which the adhesion promoter is present in vapor form , and that the metal layer is then applied with a thickness of 50-300 nm.

Vorzugsweise wird die Schicht des Haftvermittlers in einer Monomolekularschicht angebracht.The layer of the adhesion promoter is preferably applied in a monomolecular layer.

Das Substrat, mit dem das Verfahren erfolgreich durchgeführt werden kann, muss hydrophil sein oder hydrophil gemacht sein, damit eine gute Haftung mit den alkoxylierten Silangruppen hergestellt wird.The substrate with which the process can be carried out successfully must be hydrophilic or made hydrophilic in order to ensure good adhesion with the alkoxylated silane groups.

Ein Substrat aus Glas, aus Quarz oder aus Silicium, das immer mit einer natürlichen Oxidhaut bedeckt ist, hat auf der Oberfläche eine bereits ausreichende Anzahl freier OH-Gruppen, um die alkoxylierten Silangruppen zu binden unter Abspaltung von Methanol. Die meisten Kunststoffe sind an sich nicht hydrophil, können aber durch eine oxidierende Vorbehandlung hydrophil gemacht werden. Eine sehr geeignete oxidierende Behandlung, der beispielsweise Polymethylmethakrylat ausgesetzt werden kann, und die die Oberfläche derart geringfügig angreift, dass die Profilierung beibehalten wird, ist eine Glimmentladung in einer sauerstoffreichen Atmosphäre. Ein Polycarbonat kann durch eine Behandlung mit einer verdünnten Bichromatschwefelsäurelösung hydrophil gemacht werden.A substrate made of glass, quartz or silicon, which is always covered with a natural oxide skin, already has a sufficient number of free OH groups on the surface to bind the alkoxylated silane groups with the elimination of methanol. Most plastics are not hydrophilic per se, but can be made hydrophilic by an oxidizing pretreatment. A very suitable oxidizing treatment to which polymethyl methacrylate can be exposed, for example, and which attacks the surface so slightly that the profile is retained, is a glow discharge in an oxygen-rich atmosphere. A polycarbonate can be made hydrophilic by treatment with a dilute bichromate sulfuric acid solution.

Eine interessante Möglichkeit ist die Herstellung eines Spiegels mit einer ultraglatten Oberfläche. Dabei wird von einem Aluminiumsubstrat ausgegangen, dessen Oberfläche durch eine herkömmliche Bearbeitung, beispielsweise mit einer normalen Drehbank geglättet worden ist und folglich mikroskopisch gesehen eine ziemlich hohe Rauheit aufweist. Mittels einer Quarlehre, deren Oberfläche ein ultraglattes Profil hat, wird die Oberfläche des Substrates mit einem Kunststoff, beispielsweise einem Akrylat, in den Vertiefungen gefüllt, der Kunststoff wird mittles einer UV-Bestrahlung polymerisiert und auf diese Weise auf denselben hohen Glattheitsgrad gebracht wie die Quarziehre. Daraufhin wird das Substrat einer oxidierenden Vorbehandlung ausgesetzt, beispielsweise der obengenannten Glimmentladung in einer Sauerstoffatmosphäre. Dadurch werden die Kunststoffteile der Oberfläche oxidiert und es findet zugleich eine Reinigung derselben statt. Nach Anbringen des Haftvermittlers auf die bereits beschriebene Weise wird eine dünne Silber- oder Goldschicht aufgebracht, zum Beispiel durch Aufdampfen.An interesting possibility is the production of a mirror with an ultra smooth surface. The starting point is an aluminum substrate, the surface of which has been smoothed by conventional machining, for example using a normal lathe, and consequently has a fairly high roughness from a microscopic point of view. Using a quartz gauge, the surface of which has an ultra-smooth profile, the surface of the substrate is filled with a plastic, for example an acrylate, in the depressions, the plastic is polymerized by means of UV radiation and in this way brought to the same high degree of smoothness as the quartz glass . The substrate is then subjected to an oxidizing pretreatment, for example the above-mentioned glow discharge in an oxygen atmosphere. As a result, the plastic parts of the surface are oxidized and at the same time they are cleaned. After attaching the adhesion promoter in the manner already described, a thin layer of silver or gold is applied, for example by vapor deposition.

Ein derartiger Spiegel wird beispielsweise bei einem IR-Nachtsichtgerät benutzt.Such a mirror is used for example in an IR night vision device.

Die Dicke der durch Aufdampfen anzubringenden Metallschicht ist von der konkreten Ausführungsform abhängig. Beim Metallisieren des obengenannten digitalen Informationsmusters wird eine Schicht von 50-100 nm aufgedampft. Beim Metallisieren einer ultraglatten Oberfläche kann die Schicht dicker - bis 300 nm - sein.The thickness of the metal layer to be applied by vapor deposition depends on the specific embodiment. When the above-mentioned digital information pattern is metallized, a layer of 50-100 nm is deposited. When metallizing an ultra smooth surface, the layer can be thicker - up to 300 nm.

Beispiel 1example 1

Auf einer Quarzmatrize wird eine Schicht mit einer Dicke von 20 IJ.m des monomeren 4.4- lsopropylidenphenol-di- (äthylenglykolmethakry- lat)-äther, dem in einer Menge von 4 Gew. % der Fotoinitiator Benzyldimethylketal hinzugefügt worden ist, durch Aufgiessen angebracht.A layer with a thickness of 20 μM of the monomeric 4.4-isopropylidene phenol di (ethylene glycol methacrylate) ether, to which 4% by weight of the photoinitiator benzyldimethyl ketal has been added, is applied to a quartz matrix by pouring on.

Daraufhin wird die bedeckte Matrize durch Belichtung über die Quarzmatrize fotopolymerisiert. Die belichtete Schicht wird fest auf einem Aluminiumsubstrat angebracht und das Ganze wird dann von der Matrize entfernt. Dadurch ist das Substrat mit einer Kunststoffbedeckung ver-. sehen, deren Profilierung in der Oberfläche der der Matrize genau entspricht.The covered matrix is then photopolymerized by exposure to the quartz matrix. The exposed layer is firmly attached to an aluminum substrate and the whole is then removed from the die. As a result, the substrate is covered with a plastic covering. see whose surface profile exactly corresponds to that of the die.

Die hydrophobe Kunststoffoberfläche wird daraufhin durch eine Glimmentladung in einem Saüerstoffplasma während 30 Minuten mit einer Wechselspannung von 3-4 kV hydrophil gemacht. Der Gegenstand wird daraufhin. in einen Exsikkator gestellt, in welchem eine Schale mit 3-Mercaptopropyltrimethoxysilan (= trimethoxysilylpropylthiol-3) steht und ein Druck von 133 mbar eingestellt ist. Die partielle Dampfspannung des 3-Mercaptopropyltrimethoxysilan reicht aus, um mit der hydrophilen Oberfläche des Gegenstandes zu reagieren. Nach 20 Stunden Verweilzeit im Exsikkator, die eine monomolekulare Schicht dieser Verbindung erzeugt, wird der Gegenstand demselben entnommen und es wird eine Goldschicht mit einer Dicke von 0,05-0,3 4m auf bekannte Weise durch Aufdampfen angebracht.The hydrophobic plastic surface is then released by a glow discharge in a Saü made plasma hydrophilic for 30 minutes with an alternating voltage of 3-4 kV. The object is thereupon. placed in a desiccator in which a bowl with 3-mercaptopropyltrimethoxysilane (= trimethoxysilylpropylthiol-3) is placed and a pressure of 133 mbar is set. The partial vapor tension of the 3-mercaptopropyltrimethoxysilane is sufficient to react with the hydrophilic surface of the object. After a residence time of 20 hours in the desiccator, which produces a monomolecular layer of this compound, the object is removed therefrom and a gold layer with a thickness of 0.05-0.3 4 m is applied in a known manner by vapor deposition.

Das Haftvermögen der Goldschicht auf der Kunststoffoberfläche wird entsprechend dem sogenannten « Diamant-Kratzverfahren » (DIN 53 151) wie folgt geprüft.The adherence of the gold layer to the plastic surface is tested according to the so-called «diamond scratching method» (DIN 53 151) as follows.

Es werden 12 Ritzlinien durch die Metallschicht hindurch eingekratzt. Das Muster von Ritzlinien besteht aus 6 parallelen Ritzlinien in einem Abstand von 1 mm voneinander, die durch ebenfalls 6 parallele Ritzlinien in einem Abstand von 1 mm voneinander senkrecht gekreuzt werden, so dass das eingekratzte Muster 25 quadratische Flächen von 1 mm2 umfasst. Ein Klebestreifen wird auf das Muster gedrückt und danach von der Oberfläche abgerissen. Das Haftvermögen wird durch die folgenden Bewertungsnoten angegeben, wo-

  • bei 0 = optimalem Haftvermögen entspricht : 0 Quader werden von der Oberfläche abgezogen
  • 1 = gutes Haftvermögen : 1-5 Quader lösen sich
  • 2 = relativ gutes Haftvermögen : 6-10 Quader lösen sich
  • 3 = unzureichendes Haftvermögen : 11-15 Quader lösen sich
  • 4 = schlechtes Haftvermögen : 16-20 Quader lösen sich
  • 5 = kein Haftvermögen : 21-25 Quader lösen sich.
12 scratch lines are scratched through the metal layer. The pattern of scribe lines consists of 6 parallel scribe lines at a distance of 1 mm from one another, which are likewise crossed perpendicularly by 6 parallel scribe lines at a distance of 1 mm from one another, so that the scratched-in pattern comprises 25 square areas of 1 mm 2 . An adhesive strip is pressed onto the pattern and then torn off the surface. Adhesion is indicated by the following ratings,
  • at 0 = optimal adhesion corresponds to: 0 cuboids are removed from the surface
  • 1 = good adhesion: 1-5 cuboids come off
  • 2 = relatively good adhesion: 6-10 cuboids come loose
  • 3 = insufficient adhesion: 11-15 cuboids come loose
  • 4 = poor adhesion: 16-20 cuboids dissolve
  • 5 = no adhesion: 21-25 cuboids detach.

Das Haftvermögen der Goldschicht auf der Kunststoffoberfläche nach dem oben angeführten Beispiel konnte mit der Bewertungsnote O (optimales Haftvermögen) bewertet werden.The adhesiveness of the gold layer on the plastic surface according to the above example could be rated with the rating grade O (optimal adhesion).

Beispiel 2Example 2

Das Verfahren aus Beispiel 1 gilt auch für dieses Beispiel mit Ausnahme davon, dass statt Gold Silber auf dem mit der Polymerschicht und dem darauf angebrachten Haftvermittler versehenen Substrat angebracht wird.The method from Example 1 also applies to this example, with the exception that instead of gold, silver is applied to the substrate provided with the polymer layer and the adhesion promoter attached to it.

Das Haftvermögen entsprechend dem beschriebenen DIN-Test war ebenfalls mit der Bewertungsnote 0 zu bewerten.The adherence according to the described DIN test was also rated with a rating of 0.

Beispiel 3Example 3

Eine Siliciumscheibe, von der eine Oberflächenschicht in Si02 umgewandelt worden ist, wird durch eine Glimmentladung auf die Weise wie im Beispiel 1 beschrieben, hydrophil gemacht und auf dieselbe Weise wie in diesem Beispiel beschrieben mit einer monomolekularen Schicht aus 3-Mercaptopropyltrimethoxysilan behandelt. Daraufhin wird eine Gold- oder Silberschicht mit einer Dicke von 0,05-0,3 IJ.m aufgedampft. Das Haftvermögen einer solchen Schicht entsprach einer Bewertungsnote 0 nach DIN 53151.A silicon wafer, a surface layer of which has been converted to Si0 2 , is rendered hydrophilic by a glow discharge in the manner described in Example 1, and treated with a monomolecular layer of 3-mercaptopropyltrimethoxysilane in the same manner as described in this example. Then a gold or silver layer with a thickness of 0.05-0.3 IJ.m is evaporated. The adhesiveness of such a layer corresponded to a rating of 0 according to DIN 53151.

Als Haftvermittler kann man mit demselben Ergebnis 3-Aminopropyltrimethoxysilan (trimethoxysilylpropylamin-3) oder 3-Mercaptopropyltrichlorsilan (= Trichlorsilylpropyl-3-Thiol) verwenden.3-Aminopropyltrimethoxysilane (trimethoxysilylpropylamine-3) or 3-mercaptopropyltrichlorosilane (= trichlorosilylpropyl-3-thiol) can be used as an adhesion promoter with the same result.

Das erreichte optimale Haftvermögen des Edelmetalls an der Siliciumscheibe bleibt unverändert, auch wenn die metallisierte Scheibe 14 Tage lang bei einer Temperatur von 170 °C erwärmt worden ist. Der grosse Unterschied in dem Ausdehnungskoeffizienten zwischen dem Si und dem Edelmetall wird also ohne weiteres durch die Haftschicht nach der Erfindung ausgeglichen.The optimum adhesion of the noble metal to the silicon wafer remains unchanged, even if the metallized wafer has been heated at a temperature of 170 ° C. for 14 days. The large difference in the coefficient of expansion between the Si and the noble metal is thus easily compensated for by the adhesive layer according to the invention.

Claims (3)

1. A method of providing a metal layer bonded to a substrate by means of a bonding agent selected from an alkoxysilylalkylthiol, an alkoxysilylalkylamine or a chlorosilylalkylthiol, characterized in that the bonding agent is provided as a monomer in a layer which is at most 15 molecules thick on said substrate surface which is already hydrophilic or is first made hydrophilic, by con- . tact with an atmosphere in which the bonding agent is present in vapour form and that the metal layer is then provided thereon by vapour deposition in a thickness from 50 to 300 nm.
2. A method as claimed in Claim 1, characterized in that the bonding agent is provided in a monomolecular layer.
3. A method as claimed in Claim 1 or 2, characterized in that a substrate surface is made hydrophilic by means of a glow discharge in an oxidizing atmosphere.
EP83201703A 1982-12-10 1983-12-01 Method of applying a metallic coating to a substrate Expired EP0111957B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL8204783A NL8204783A (en) 1982-12-10 1982-12-10 METHOD FOR APPLYING A METAL LAYER ON A SUBSTRATE
NL8204783 1982-12-10

Publications (3)

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EP0111957A2 EP0111957A2 (en) 1984-06-27
EP0111957A3 EP0111957A3 (en) 1984-07-25
EP0111957B1 true EP0111957B1 (en) 1986-07-30

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EP83201703A Expired EP0111957B1 (en) 1982-12-10 1983-12-01 Method of applying a metallic coating to a substrate

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US (1) US4521444A (en)
EP (1) EP0111957B1 (en)
JP (1) JPS59113177A (en)
CA (1) CA1219180A (en)
DE (1) DE3365017D1 (en)
NL (1) NL8204783A (en)

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US4521444A (en) 1985-06-04
EP0111957A2 (en) 1984-06-27
CA1219180A (en) 1987-03-17
EP0111957A3 (en) 1984-07-25
JPS59113177A (en) 1984-06-29
DE3365017D1 (en) 1986-09-04
NL8204783A (en) 1984-07-02
JPH039188B2 (en) 1991-02-07

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